The present invention relates to a catalyst solution for polymerizing xcex1-olefins, obtainable by
a) reacting a metallocene compound of the formula I 
xe2x80x83where the substituents have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum
X is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, xe2x80x94OR6 or xe2x80x94NR6R7,
where
R6 and R7 are C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical,
R1 to R5 are hydrogen, C1-C10-alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C1-C10-alkyl as substituent, C6-C15-aryl or arylalkyl, where two adjacent radicals may also together form a saturated or unsaturated cyclic group having from 4 to 15 carbon atoms, or Si(R8)3 where
R8 is C1-C10-alkyl, C3-C10-cycloalkyl or C6-C15-aryl,
Z is X or 
xe2x80x83where the radicals
R9 to R13 are hydrogen, C1-C10-alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C1-C10-alkyl as substituent, C6-C15-aryl or arylalkyl, where two adjacent radicals may also together form a saturated or unsaturated cyclic group having from 4 to 15 carbon atoms, or Si(R14)3 where
R14 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl,
xe2x80x83or where the radicals R4 and Z together form an xe2x80x94R15xe2x80x94Axe2x80x94 group in which
R15 is 
xe2x80x83xe2x95x90BR16, xe2x95x90AlR16, xe2x80x94Gexe2x80x94, xe2x80x94Snxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x95x90SO, xe2x95x90SO2, xe2x95x90NR16, xe2x95x90CO, xe2x95x90PR16 or xe2x95x90P(O)R16,
where
R16, R17 and R18 are identical or different and are each a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkyl-aryl group or two adjacent radicals together with the atoms connecting them form a ring, and
M2 is silicon, germanium or tin,
A 
xe2x80x83where
R19 is C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, alkylaryl or Si(R20)3,
R20 is hydrogen, C1-C10-alkyl, C6-C15-aryl which may in turn bear C1-C4-alkyl groups as sub-stituents or C3-C10-cycloalkyl
or the radicals R4 and R12 together form an xe2x80x94R15xe2x80x94 group,
with an activator compound which can react with the metallocene compound I so as to displace a ligand X from the central atom M and to stabilize the resulting cationic complex by means of a non-coordinating anion as ion pair,
b) adding one or more xcex1-olefins in a molar ratio of metallocene compound I: xcex1-olefin of from 1:1 to 1:100 and
c) mixing with at least 10 parts by volume of an aliphatic hydrocarbon.
The present invention further relates to a process for polymerizing xcex1-olefins in the presence of this catalyst solution and also to the use of this catalyst solution for the polymerization of xcex1-olefins.
The cationic activation of metallocene complexes to form active catalyst compounds has been described in numerous publications. In these reactions, the metallocene complex is reacted with an ion-exchange component, eg. a cation or a Lewis acid which is able to irreversibly react with one of the complexing ligands, and a non-coordinating anion which can stabilize the resulting cationic metallocene complexes. The structure of many metallocene complexes, but in particular the structure of the activating reagents and of the ion pairs of cationic metallocene complex and anionic non-coordinating counterion formed during the course of the activation, makes moderately polar solvents generally necessary for this reaction, for example aromatic or halogenated hydrocarbons. Thus, EP-A-709 393 describes the cationic activation of metallocene complexes having substituted fluorophenyl ligands in toluene as solvent. WO-93/25590 likewise describes the cationic activation of metallocene complexes, with preference being given to using aromatic solvents, in particular toluene (see examples) for these reactions. The linear, branched or alicyclic hydrocarbons which are likewise mentioned for this purpose have generally been found to be unsuitable for this purpose since they have only insufficient solvent capability for, in particular, the cationic metallocene complexes and the activation reagents.
The cationically activated metallocene complexes can also be advantageously used in unsupported form in slurry or solution polymerization processes. Solvents which have been found to be suitable for these polymerization processes, in particular for polymerization processes at high temperature and high pressure, are, in particular, aliphatic solvents, in particular saturated hydrocarbons. In contrast, aromatic and halogenated hydrocarbons have disadvantages which are presumably attributable to their reactivity and to a destruction or blocking of the catalyst by these compounds. In polymerizations in these solvents, a lower catalyst productivity, a greater need for alkyl compounds for eliminating impurities and an increased proportion of wax-like by-products in the polymers are observed. However, the unsatisfactory solubility of cationically activated metallocene catalysts in aliphatic solvents has hitherto usually made the use of aromatic solvents necessary in such solution polymerization processes.
It is an object of the present invention to increase the solubility of cationically activated catalyst complexes so that they have sufficient solubility in aliphatic solvents.
We have found that this object is achieved by the catalyst solution described in the introduction for polymerizing xcex1-olefins, a process for polymerizing xcex1-olefins in the presence of this catalyst solution and the use of this catalyst solution for the polymerization of xcex1-olefins.
Among the metallocene complexes of the formula I, preference is given to 
Particular preference is given to those transition metal complexes which have two aromatic ring systems bridged to one another as ligands, ie. in particular the transition metal complexes of the formula Ic.
The radicals X can be identical or different; they are preferably identical.
Among the compounds of the formula Ia, particular preference is given to those in which
M is titanium, zirconium or hafnium,
X is C1-C4-alkyl or phenyl and
R1 to R5 is hydrogen or C1-C4-alkyl.
Among the compounds of the formula Ib, preference is given to those in which
M is titanium, zirconium or hafnium,
X is C1-C4-alkyl or phenyl,
R1 to R5 is hydrogen, C1-C4-alkyl or Si(R8)3,
R9 to R13 is hydrogen, C1-C4-alkyl or Si(R14)3.
In particular, suitable compounds of the formula Ib are those in which the cyclopentadienyl radicals are identical.
Examples of particularly suitable compounds are, inter alia, those which are derived from the following compounds II:
bis(cyclopentadienyl)zirconium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride,
bis(ethylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dichloride and
bis(trimethylsilylcyclopentadienyl)zirconium dichloride
and also the corresponding dimethylzirconium compounds.
Particularly suitable compounds of the formula Ic are those in which
R1 and R9 are identical and are hydrogen or C1-C10-alkyl groups,
R5 and R13 are identical and are hydrogen, methyl, ethyl, isopropyl or tert-butyl,
R2, R3, R10 and R11 have the meanings: R3 and R11 are C1-C4-alkyl, R2 and R10 are hydrogen, or two adjacent radicals R2 and R3 or R10 and R11 together form a cyclic group having from 4 to 12 carbon atoms,
R15 is 
M is titanium, zirconium or hafnium and
X is C1-C4-alkyl or phenyl.
Examples of particularly suitable complexes are, inter alia, those which are derived from the following compounds II:
dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(indenyl)zirconium dichloride,
dimethylsilanediylbis(tetrahydroindenyl)zirconium dichloride,
ethylenebis(cyclopentadienyl)zirconium dichloride,
ethylenebis(indenyl)zirconium dichloride,
ethylenebis(tetrahydroindenyl)zirconium dichloride,
tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride,
dimethylsilanediylbis(3-tert-butyl-5-methylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-tert-butyl-5-ethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2-methylindenyl)zirconium dichloride,
dimethylsilanediylbis(2-isopropylindenyl)zirconium dichloride,
dimethylsilanediylbis(2-tert-butylindenyl)zirconium dichloride,
diethylsilanediylbis(2-methylindenyl)zirconium dibromide,
dimethylsilanediylbis(3-methyl-5-methylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-ethyl-5-isopropylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2-methylindenyl)zirconium dichloride,
dimethylsilanediylbis(2-methylbenzindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethylbenzindenyl)zirconium dichloride,
methylphenylsilanediylbis(2-ethylbenzindenyl)zirconium dichloride,
methylphenylsilanediylbis(2-methylbenzindenyl)zirconium dichloride,
diphenylsilanediylbis(2-methylbenzindenyl)zirconium dichloride,
diphenylsilanediylbis(2-ethylbenzindenyl)zirconium dichloride, and
dimethylsilanediylbis(2-methylindenyl)hafnium dichloride
and also the corresponding dimethylzirconium compounds.
Particularly suitable compounds of the formula Id are those in which
M is titanium or zirconium,
X is C1-C4-alkyl or phenyl,
R15 is 
A is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, 
and
R1 to R3 and R5 are hydrogen, C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl or Si(R8)3, or two adjacent radicals form a cyclic group having from 4 to 12 carbon atoms.
The synthesis of such complexes can be carried out using methods known per se, with preference being given to reacting the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum.
Examples of appropriate preparative methods are described, inter alia, in Journal of Organometallic Chemistry, 369 (1989), 359-370.
It is also possible to use mixtures of various metallocene complexes.
Suitable activator compounds are strong, uncharged Lewis acids, ionic compounds having Lewis acid cations and ionic compounds having Brxc3x6nsted acids as cation.
As strong, uncharged Lewis acids, preference is given to compounds of the formula III
M3X1X2X3xe2x80x83xe2x80x83III
where
M3 is an element of main group III of the Periodic Table, in particular B, Al or Ga, preferably B,
X1, X2 and X3 are hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine, in particular haloaryls, preferably pentafluorophenyl.
Particular preference is given to compounds of the formula III in which X1, X2 and X3 are identical, preferably tris(pentafluorophenyl)borane.
Suitable ionic compounds having Lewis acid cations are compounds of the formula IV
[(M4a+)Q1Q2 . . . Qz]d+xe2x80x83xe2x80x83IV
where
M4 is an element of main groups I to VI or transition groups I to VIII of the Periodic Table,
Q1 to Qz are singly negatively charged radicals such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms in the aryl radical and from 1 to 28 carbon atoms in the alkyl radical, C1-C10-cycloalkyl which may bear C1-C10-alkyl groups as substituents, halogen, C1-C28-alkoxy, C6-C15-aryloxy, silyl or mercaptyl groups,
a is an integer from 1 to 6,
z is an integer from 0 to 5 and
d is the difference axe2x88x92z, but d is greater than or equal to 1.
Particularly suitable Lewis acid cations are carbonium cations, oxonium cations and sulfonium cations and also cationic transition metal complexes. Particular mention may be made of the triphenylmethyl cation, the silver cation and the 1,1xe2x80x2-dimethylferrocenyl cation. They preferably have non-coordinating counter-ions, in particular boron compounds as are also mentioned in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.
Ionic compounds having Br6nsted acids as cations and likewise non-coordinating counter ions are mentioned in WO 91/09882; the preferred cation is the N,N-dimethylanilinium cation.
The solubility of the cationically activated metallocene compound in aliphatic solvents is drastically increased by the reaction step b), ie. by reaction with a small amount of one or more xcex1-olefins. A wide variety of xcex1-olefins can be used, preferably those having from 2 to 20 carbon atoms. These xcex1-olefins can be linear or branched. Particular preference is given to adding butene, hexene or octene. Mixtures of any of the xcex1-olefins mentioned can also be used.
The xcex1-olefins are used either in an equimolar ratio or in an excess of up to 100-fold based on the metallocene compound I. Even a small excess of xcex1-olefins significantly increases the solubility of the complex in aliphatic solvents. Particularly in the case of relatively long-chain xcex1-olefins, for instance those having from 6 to 12 carbon atoms, addition of an equimolar amount is often sufficient, but in the case of shorter xcex1-olefins an excess is advisable. The molar ratio of metallocene compound I: xcex1-Olefin in step b) is preferably from 1:1 to 1:10.
In reaction step a), ie. the activation of the metallocene complex I, a moderately polar solvent is usually necessary in order to keep all reaction components sufficiently dissolved in a very small volume. The preparative step a) is preferably carried out in the presence of an aromatic or halogenated hydrocarbon, particularly preferably in the presence of toluene or xylene.
The reaction with the xcex1-olefin is generally carried out at from xe2x88x9290 to 150xc2x0 C., preferably from 30 to 110xc2x0 C., with the reaction time being at least 0.1 sec.
After the activation of the metallocene complex I and the reaction with the xcex1-olefin, the reaction mixture is mixed with at least 10 parts by volume of an aliphatic hydrocarbon. This mixing can be carried out directly in combination with the subsequent polymerization reaction, ie. for example by introducing the reaction mixture from step b) into a polymerization vessel and diluting it appropriately there. This dilution can be carried out before addition of the olefin to be polymerized, but an olefin/solvent mixture can also be charged initially so that the polymerization can commence simultaneously with the dilution of the reaction mixture from step b). However, it is also possible and for practical reasons often advantageous to carry out the dilution of the reaction mixture from step b) using at first only the appropriate amount of the aliphatic solvent. This gives a storage-stable, active catalyst solution which can be used at a later point in time in a customary manner for polymerization reactions.
In order to make full use of the advantages of the catalyst solution of the present invention, the reaction mixture from step b) has to be mixed with at least 10 parts by volume of an aliphatic hydrocarbon before use in the later polymerization process. An even greater dilution volume can be advantageous for process reasons. In any case, good results are achieved by dilution with from 10 to 1000, preferably from 10 to 100, parts by volume. In this context, the term hydrocarbon also includes mixtures of various hydrocarbons.
The metallocene compound I can be prepared in various ways with which those skilled in the art are familiar. An advantageous synthesis starts from metallocene compounds of the formula II. It is particularly advantageous if the reaction to produce the metallocene compound I is carried out in situ by reacting a metallocene compound of the formula II 
where R1, R2, R3, R4, R5, M and Z are as defined above and
Y is fluorine, chlorine, bromine or iodine,
with an appropriate alkyl of a metal of main group I, II or III of the Periodic Table and the resulting solution is reacted further in step a) without purification.
As alkyl of a metal of main group I, II or III of the Periodic Table, it is possible here to use any alkyl compound customarily used for the alkylation of metallocene complexes. Preference is given to using aluminum alkyls such as triisobutylaluminum for this purpose.
The catalyst solution of the present invention can be used in all customary polymerization processes for the polymerization or co-polymerization of xcex1-olefins, if desired with other vinylic monomers. It can also be used to prepare supported catalysts. However, the advantages of the catalyst solution of the present invention are particularly apparent in processes for polymerizing xcex1-olefins in the presence of this catalyst solution, in which the polymerization is carried out in solution with an essentially aliphatic solvent.
Both pure hydrocarbons and hydrocarbon mixtures are useful as solvents here. Examples which may be mentioned are hexane, heptane, octane, nonane, decane, dodecane and isododecane, where both linear and branched isomers as well as their mixtures can be used.
The catalyst solution of the present invention can be used particularly advantageously in solution polymerizations, eg. in autoclave processes and in high-pressure processes, with the latter preferably being carried out in tube reactors.
Preference is given to processes for polymerizing xcex1-olefins, in which the polymerization is carried out at from 160 to 350xc2x0 C. and at pressures of from 500 to 3500 bar. Particularly preferred temperatures for these processes are from 180 to 240xc2x0 C., particularly preferred pressures are from 1400 to 2000 bar. Further details for carrying out such polymerizations in high-pressure reactors are described, for example, in xe2x80x9cUllmann""s Encyklopxc3xa4die der technischen Chemiexe2x80x9d, Verlag Chemie, Weinheim, Volume 19, (1980), pages 169 to 195.
The polymerization process of the present invention enables various xcex1-olefins to be polymerized. In this context, polymerization includes both homopolymerization and copolymerization of different xcex1-olefins or of xcex1-olefins with other vinylic comonomers such as styrene. The catalyst solution is particularly useful in processes for polymerizing xcex1-olefins in which ethylene or a mixture of ethylene and subordinate amounts of further C1-C8-xcex1-olefins is used as xcex1-olefin. These C1-C8-xcex1-olefins are generally present in the corresponding copolymers in amounts of 0.5-10% by weight.
The use of the catalyst solution of the present invention for the polymerization of xcex1-olefins has various advantages: the solubility and miscibility with aliphatic solvents makes the presence of relatively large amounts of aromatic or halogenated solvents unnecessary. The catalyst complex is therefore more stable and has a longer shelf life. Fewer termination reactions are observed and thus smaller proportions of wax-like polymers are obtained in the polymerization products. The polymers obtained therefore have particularly good homogeneity. In addition, the catalyst solutions of the present invention display better productivities than corresponding catalyst solutions based on toluene.